Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof

Definitions

• This invention relates to the preparation of acetaldehyde and is more particularly concerned with the preparation of acetaldehyde by conversion of acetic anhydride.
• Acetaldehyde is a well-known chemical of commerce, used primarily as an intermediate in the production of organic chemicals, and has been produced commercially for many years, for example by the hydration of acetylene and the catalytic oxidation of ethyl alcohol, ethylene and saturated hydrocarbons such as butane. More recently it has been discovered that acetaldehyde can be produced by the action of carbon monoxide and hydrogen upon alcohols, ethers and esters in the presence of catalysts based on metals of the 8th Group of the Periodic Table. Such reactions are described, for example, in Reppe et al. U.S. Pat. No. 2,727,902, Butter U.S. Pat. No.
• Fenton U.S. Pat. No. 3,579,566 treats organic acid anhydrides such as acetic anhydride with hydrogen in the presence of a catalyst comprising a complex of a Group VIII noble metal with a biphyllic ligand from the group consisting of trihydrocarbyl phosphines, arsines and stibines.
• the Fenton examples show the preparation primarily of ethylidene diacetate from acetic anhydride by this technique. Small amounts of acetaldehyde are also reported by Fenton but the amounts produced are inadequate when it is desired to have acetaldehyde as the principal product along with acetic acid. Belgian Pat. No.
• 879,178 converts anhydrides to 1,1-diesters with hydrogen in the presence of certain supported metals, including metals of Group VIII of the Periodic Table, and in the presence of a strong protonic acid such as hydrochloric and hydrofluoric acids. No formation of acetaldehyde is shown.
• an object of this invention to provide a process for the preparation of acetaldehyde in which the selectivity to acetaldehyde is significantly increased and in which the reaction can be carried out at moderately elevated pressures.
• the mol ratio of hydrogen to acetic anhydride be at least 5:1. Operation at lower ratios can, however, be carried out since acetaldehyde is still produced in substantial amounts, but ordinarily the ratio is suitably at least 1:1. The upper limit is governed only by economic considerations.
• the mol ratio of hydrogen to acetic anhydride is at most 100:1, most preferably 50:1.
• the Group VIII noble metal catalyst is supplied and used in supported form, i.e., carried on or dispersed on a support or carrier which is of such size that it can be employed in fixed or fluidized bed reactors, e.g., from 400 mesh/inch to 1/2-inch particle sizes.
• the range of variation of the pore volume relative to solid weight is from 0.03 to 2.5 cm 3 /gram of the porous phase, with a preferred range of from 0.05 to 1.5 cm 3 /gram.
• carrier materials can be used, as exemplified by pumice, alumina, silica, silica-alumina, aged or deactivated silica-alumina cracking catalyst, magnesia, diatomaceous earth, bauxite, titania, zirconia, clays, both natural and acid treated such as Super-Filtrols, attapulgus clay (attapulgite), lime, magnesium silicate, silicon carbide, activated and unactivated carbons, zeolites as well as the zeolitic molecular sieves, solid foams, such as ceramic honeycombs, and porous organic polymers.
• the above carriers are used as regular and irregular particles and as capillary tubes, and interspacing elements such as shapes, extrudates, ceramic rods, balls, broken pieces, tiles, and the like, disposed within the reactor.
• the catalyst component can be applied to the carrier in conventional manner, e.g., by impregnation of the carrier with a solution of a soluble compound of the Group VIII noble metal, e.g., a halide, nitrate or the like, followed by drying. If desired, the catalyst can be pre-activated, for example, by heating it in the presence of hydrogen. Catalyst component concentration upon the carrier may vary widely, e.g., 0.01 weight percent to 10 weight percent, or higher.
• the hydrogen is preferably employed in substantially pure form as available commercially, but inert diluents such as nitrogen, methane, and noble gases can be present if desired.
• inert diluents such as nitrogen, methane, and noble gases can be present if desired.
• the presence of inert diluents does not affect the reaction but their presence makes it necessary to increase the total pressure in order to maintain the desired hydrogen partial pressure.
• the hydrogen is preferably substantially free of CO.
• the hydrogen should also be essentially dry, i.e., the hydrogen and the other reactants should be reasonably free from water. The presence of minor amounts of water such as may be found in the commercial forms of the reactants is, however, entirely acceptable.
• the temperature of the reaction mixture is selected to keep the reactants and the reaction products continuously in the vapor-phase as they pass over the catalyst bed in the vapor-phase reactor at the total pressure and total gas flow rate employed. Ordinarily, the temperature will lie within the range of 140° and 225° C. Higher temperatures can be employed but there is no particular advantage in their use.
• the time of reaction is not a parameter of the process and depends largely upon the temperature employed, but typical volume space velocities, by way of example, will generally fall in the range of 500 to 10,000 hr. -1 .
• the reaction is carried out under superatmospheric pressure but excessively high pressures, which require special high-pressure equipment, are not necessary.
• the reaction is effectively carried out by employing a hydrogen partial pressure which is preferably 30 to 3,000 psi, although a hydrogen partial pressure within the broader range of 10 to 10,000 psi can also be employed.
• the total pressure is that required to provide the desired hydrogen partial pressure and to maintain the vapor phase. Typically, up to about 3,500 psig are used.
• the reaction can be advantageously carried out in a conventional fluid-bed or fixed-bed reactor.
• the effluent from the reaction zone is entirely gaseous, i.e., it is composed of the non-condensible gases in the reaction system, e.g., hydrogen, as well as vaporized organic compounds including the product acetaldehyde, unreacted acetic anhydride, and acetic acid.
• the non-condensible gases in the reaction system e.g., hydrogen
• vaporized organic compounds including the product acetaldehyde, unreacted acetic anhydride, and acetic acid.
• the vaporous reaction mixture is continuously removed from the reaction zone and partially condensed to separate the higher boiling constituents and to provide a net product consisting of acetaldehyde which is then separately condensed or otherwise recovered, to remove it from the non-condensible gas component, e.g., hydrogen.
• the reactants e.g., acetic anhydride and hydrogen
• the other components of the vapor effluent both gaseous and liquid, particularly unreacted acetic anhydride and hydrogen, can be continuously recycled to the reaction zone.
• the Group VIII noble metal catalyst remains in the reaction zone at all times and only the vaporous effluent is removed.
• a purge of the recycled gases may be taken in conventional manner to prevent the build-up of contaminating gases which may have been present in the hydrogen feed to the system such as nitrogen or may have been produced in the reaction itself.
• a reactor which is in the form of a one ft. tube having an internal diameter of 5/8 in. and provided with a temperature controller, a thermocouple, a pressure controller, a preheater, a feed inlet and a gas outlet leading to a series of condensers.
• the reactor tube is filled to a depth of 5 in. with 20 cc. (19 grams) of palladium supported (5 wt. %) on 1/8" pellets of alumina. Hydrogen and vaporized acetic anhydride (premixed and vaporized in the preheater) are passed into the reactor for 2 hours at a temperature of 185° C.
• Example 1 is repeated with the exception that the pressure is maintained at 60 psig and the effluent vapors exiting from the condensers are passed through a scrubber at -80° C. containing a liquid for absorbing additional acetaldehyde, i-propyl alcohol in this case but other liquids such as ethylbenzene, ethyl alcohol, acetone and the like can be used. Selectivity to acetaldehyde is found to be 85% and the acetaldehyde to acetic acid ratio is 0.84. No ethylidene diacetate is detected.
• Example 2 is repeated but the hydrogen feed rate is changed to 27 liters per hour. Analysis shows a selectivity to acetaldehyde of 81% and an acetaldehyde to acetic acid ratio of 0.91. Ethylidene diacetate is detected representing a selectivity to this compound of 1.2%.
• Example 3 is repeated except that the pressure is further reduced to 30 psig. Analysis shows a 76% selectivity to acetaldehydeand an acetaldehyde to acetic acid ratio of 0.71. No ethylidene diacetate is detected.
• Example 2 is repeated but at a temperature of 160° C. Analysis shows a selectivity to acetaldehyde of 96% and an acetaldehyde to acetic acid ratio of 0.94. Only a trace of ethylidene diacetate is detected.
• Example 2 is again repeated at a temperature of 150° C., a pressure of 60 psig, an acetic anhydride feed rate of 13.4 cc. per hour and a hydrogen feed rate of 77 liters per hour, the process being carried out for 4 hours.
• Analysis shows a selectivity to acetaldehyde of 99% and an acetaldehyde to acetic acid ratio of 0.99. No ethylidene diacetate is detected.
• Example 7 is repeated at a pressure of 100 psig, an acetic anhydride feed rate of 13.7 cc. per hour and a hydrogen feed rate of 108 liters per hour, the process being carried out for 3 hours. Analysis shows a selectivity to acetaldehyde of 73% and an acetaldehyde to acetic ratio of 0.84. Only a trace of ethylidene diacetate is detected.
• the catalyst is 20 cc. (9.2 g.) of 1% palladium on activated carbon (4 ⁇ 8 mesh size).
• reaction is carried out at a temperature of 185° C., a pressure of 30 psig, an acetic anhydride feed rate of 12.5 cc. per hour and a hydrogen feed rate of 77 liters per hour, the process being carried out for 2 hours.
• Analysis shows a selectivity to acetaldehyde of 93% and an acetaldehyde to acetic acid ratio of 1. Only a trace of ethylidene diacetate is detected.
• Example 8 is repeated at a temperature of 150° C., a pressure of 30 psig, an acetic anhydride feed rate of 12.5 cc. per hour and a hydrogen feed rate of 77 liters per hour, the process being carried out for 2 hours.
• Analysis shows a selectivity to acetaldehyde of 86% and an acetaldehyde to acetic acid ratio of about 1. Selectivity of ethylidene diacetate is 0.6%.
• Example 8 is again repeated at a temperature of 185° C., a pressure of 60 psig, an acetic anhydride feed rate of 12.5 cc. per hour and a hydrogen feed rate of 77 liters per hour, the process being carried out for 2 hours.
• Analysis shows a selectivity to acetaldehyde of 91% and an acetaldehyde to acetic acid ratio of 0.98.
• Selectivity to ethylidene diacetate is 0.2%.
• Example 8 is repeated at a temperature of 150° C., a pressure of 60 psig, an acetic anhydride feed rate of 12.5 cc. per hour and a hydrogen feed rate of 77 liters per hour, the process being carried out for 2 hours.
• Analysis shows a selectivity to acetaldehyde of 83% and an acetaldehyde to acetic acid ratio of 0.93.
• Selectivity to ethylidene diacetate is 2%.
• Example 8 is again repeated at a temperature of 150° C., a pressure of 60 psig, an acetic anhydride feed rate of 23.5 cc. per hour and a hydrogen feed rate of 77 liters per hour, the process being carried out for 2 hours.
• Analysis shows a selectivity to acetaldehyde of 91% and an acetaldehyde to acetic acid ratio of 0.98.
• Selectivity to ethylidene diacetate is 4.8%.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Citations (6)

• 1980
  • 1980-10-06 US US06/194,324 patent/US4356328A/en not_active Expired - Lifetime
• 1981
  • 1981-09-29 NL NL8104445A patent/NL8104445A/nl not_active Application Discontinuation
  • 1981-09-30 FR FR8118438A patent/FR2491459A1/fr active Granted
  • 1981-10-05 IT IT49427/81A patent/IT1143226B/it active
  • 1981-10-05 BR BR8106408A patent/BR8106408A/pt unknown
  • 1981-10-05 BE BE0/206168A patent/BE890630A/fr not_active IP Right Cessation
  • 1981-10-06 GB GB8130137A patent/GB2084582B/en not_active Expired
  • 1981-10-06 JP JP56159364A patent/JPS5791942A/ja active Pending
  • 1981-10-06 DE DE3139708A patent/DE3139708C2/de not_active Expired
  • 1981-10-06 ZA ZA816917A patent/ZA816917B/xx unknown
  • 1981-10-06 MX MX189504A patent/MX151837A/es unknown

Patent Citations (6)

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